The new deal is multi-territory, multi-property and multi-category.
Warner Bros Consumer Products' latest agreement grants Primark the licence to produce apparel ranges across a range of brands including Looney Tunes, DC Comics - Superman, Batman and Wonderwoman, - Scooby Doo, The Flintstones and Tom & Jerry.
All product areas are covered in the deal and items will be available in up to 221 Primark stores across Europe including the 153 outlets with further distribution in Ireland, Spain, Portugal, Germany, Netherlands and Belgium.
Paul Bufton, general manager, WBCP UK, said: "To date we've seen great presence for our brands in Primark and this is an exciting extension of out successful partnership. Primark is committed to producing quality, on-trend apparel that embraces the core values of our brands.
"The retailer is a dominant force on the High Street and it welcomes millions of customers into its stores every day, the potential to drive sales and consumer awareness for our brands is incredible."
Paul Marchant, chief executive, Primark, added: "This is a very exciting opportunity for Primark to work directly with Warner Bros. This agreement will allow us to offer Primark customers a combination of great fashion and design, showcasing Warner Bros brands, at amazing Primark prices."